Gluconic acid salts of certain oxyalkylated amine-modified thermoplastic phenol-aldehyde resins, and method of making same



United States Patent Ofiice 2,839,502 Patented June 17, 1958 GLUCONIC ACID SALTS i'JERTAIN OXYALKYL- ATED AMINE NIGDLFIED THERMOPLASTIC PHENQL-ALDEi-IYDE RESINS, AND METHOD OF MAKING SAME Melvin De Groote, St. Louis, Mo., assignor to Petrolite Corporation, itilmington, Del., a corporation of Delaware No Drawing. Original application January 26, 1953, Se rial No. 333,388, new l atent No. 2,771,447, dated November 20, 1956. Divided and this application April 9, 1956, Serial No. 576,824

13 Claims. (Cl. 260-53) The present invention is a continuation-in-part of my five co-pending applications, Serial No. 288,744, filed May 19, 1952, now abandoned; Serial No. 296,085, filed June 27, 1952, now U. S. Patent 2,679,486; Serial No. 301,805, filed July 30, 1952; Serial No. 310,553, filed September 19, 1952, now U. 8. Patent 2,695,889; Serial No. 329,484, filed January 2, 1953; and a division of my co-pending application Serial No. 333,388, filed January 26, 1953, Patent No. 2,771,447.

My invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type and particularly petroleum emulsions. My invention is also concerned with the application of such chemical products or compounds in various other arts and industries as Well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification.

My aforementioned co-pending application, Serial No. 301,805, filed July30, 1952, Patent No. 2,743,253 is concerned with the process of first condensing certain phenol-aldehyde resins, therein described in detail, with certain basic non-hydroxylated polyamines, therein described in detail, and formaldehyde, which condensation is followed by oxyalkylation with certain monoepoxides, also therein described in detail.

The present invention is concerned with the aforementioned amino resin condensate in the form of a gluconic acid salt, i. e., a form in which part or all the basic nitrogen atoms are neutralized with gluconic acid, i. e., converted into the salt of gluconic acid.

My aforementioned co-pending-application, Serial No. 310,553 filed September 19, 1952, is concerned-with a process for breaking petroleum emulsions of the waterin-oil type characterized by subjecting the emulsion to the action of a demulsifier including the amine resin condensates described in the aforementioned application Serial No. 301,805, Patent No. 2,743,253.

Needless to say, all that is required is to prepare the amine oxyalkylated resin condensates in the manner described in the two aforementioned co-pending applications, and then neutralize with gluconic acid which, for practical purposes is as simple as analogous inorganic reactions.

As far as the use of the herein described products goes for purposes of resolution of petroleum emulsions of the water-in-oil type, I particularly prefer to use the gluconic acid salt of those members which have sufiicient hydrophile character to meet at least the test as set forth in U. S. Patent No. 2,499,368 dated March 7, 1950 i to De Groote et al. In said patent such. test for emulsification using a waterinsoluble solvent, generally xylene, is described as an index of surface activity.

The present invention involves the surface-activity of the gluconic acid salts, i. e., either where only one basic amino nitrogen atom is neutralized or where all basic amino nitrogen atoms are neutralized. Such gluconic acid salts may not necessarily be xylene soluble. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For convenience, what is said hereinafter will be divided into eight parts:

Part 1 is concerned with the general structure of the amine-modified resins which after oxyalkylation are converted to the gluconic acid salt;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin;

Part 3 is concerned with appropriate basic secondary polyamines free from ,a hydroxyl radical which may be employed in the preparation of the herein described amine-modified resins;

Part 4 is concerned with reactions involving the resin, the polyamine, and formaldehyde to produce specific products or compounds which are then subjected to oxyalkylation;

Part 5 is concerned with the oxyalkylation of the products described in Part 4 preceding;

Part 6 is concerned with the conversion of the basic oxyalkylated derivatives described in Part 5, preceding,

in the corresponding salt of gluconic acid;

Part 7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the pre-. viously described chemical compoundsor reaction products in the form of gluconic acid salts; and

Part 8 is concerned with uses for the products herein described, either as such or after modification, including any applications other than those involving resolu+ tion of petroleum emulsions of the water-in-oil type. This part is limited also to the use of the gluconic acid salts.

For reasons which are obvious, particularly for convenience and ease of comparison, the various parts are in substantially verbatim form as they appear in one or more of the aforementioned co-pending applications, to wit, Serial Nos. 288,744, 296,085, 301,805, 310,553, and 329,484. For example, Parts 1, 2, 3 and 4 are substantially as they appear in co-pending application, Serial No. 329,484, filed January 2, 1953; Part 5 is substantially the same as it appears in aforementioned co-pending application, Serial No. 301,805, filed July 30, 1952, and Serial No. 310,553, filed September 19, 1952. Part 6 corresponds approximately to what appears in Serial No. 329,484, filed January 2, 1953. i

PART 1 The compounds herein described and particularly useful as demulsifying agents are gluconic acid salts of heatstable and oXyalkylation-susceptible resinous condensation products obtained by oxyalkylating the amine resin condensates described in applications Serial Nos. 288,744

and 296,085 to which reference is made for a discussion.

61 to present certain resin structure. Such formula would be the following:

in which Rrepresents an aliphatic hydrocarbon substituent generally having four and not over 18 carbon atoms but most preferably not over 14 carbon atoms, and n generally is a small whole number varying from 1 to 4. In the resin structure it is shown as beingderived from formaldehyde although obviously othcr aldehydes are equally satisfactory. The amine residue in the above structure is derived from a non hydroxylated basic polyamine and usually a strongly basic polyamine having at least one secondary'amin'o radical and free from any primary amino radical, any substituted imidazolin'e radical and any substituted tetrahydropyrimidine radical, and maybeindicated thus:

in which R represents any appropriate hydrocarbon radical, such as an alkyl, alicyclic, a'rylalkyl radical, etc., free from hydroxyl radicals, withthe proviso that at least one occurrence of R"contai ns an amino'radical which is not part of a'primary amino radical or part of a substituted imidazoline radical or part of a substituted tetrahydropyrimidine radical.

Actually, what has been depicted in the formula immediately above is only an over-simplified exemplification of that part of the polyamine which has the reactive secondary amino group. Actually, a more complete illustration is obtained by reference to substitutedpoly'alkylene amines of the followingstnucture:

R R N.CnHr-(C,.H2,.H.D)N R n" in which R has its prior significance, R" represents a hydrogen atom or radical R,-D is a hydrogen atomor an alkyl group, n 'representsthe numerals l'to l0, and x rep resents a small Whole number varying from 1 to 7 but generally from 1 toS, with the proviso that the other previously stated requirements are met. See U. S. Patent No. 2,250,176 dated July 22, 1941, to "Blair.

See also U. S. Patent No. 2,362,464 dated November 14, 1944, to Britton et al., which describes alkylene diamines and p'olymethylene diamines having the'formula GHQ-CH2 N-G,.H,,.-NH,

cHrfOz wherein n is a whole number from 2 to 12 inclusive, and

the nitrogen atoms are separated by at least two carbon atoms, into a secondary amine by means of an alkylating agent such as dimethyl sulfate, benzyl chloride, an alkyl bromide, an ester of a sulfonic acid, etc., so as to yield a compound such as The introduction of two such polyamine radicals into a comparatively small resin molecule, for instance, one having 3 to 6 phenolic nuclei as specified, alters the resultant product in a number of ways. In the first place, a basic nitrogen atom, of course adds a hydrophile efiect; in the second place, depending on the size of the radical R, there may be a counterbalancing hydrophobe effect or one in which the hydrophobe effect more than counterbalances the hydrophile effect of the nitrogen atom. Finally, in such cases where R contains one or more oxygen atoms, another effect is introduced, particularly another hydrophile effect.

The resins employed as raw materials in the instant procedure are characterized by the presence of an aliphatic radical in the ortho or para position, i. e., the

phenols themselves are difunctional phenols.

The resins herein employed contain only two terminal groups which are reactive to formaldehyde, i. e., they are difunctional from the standpoint of methylol-forming re actions. As is well known, although one may start with diiunctiona-l phenols, and depending on the procedure employed, one may obtain'cross-linking which indicates that one or more of the phenolic nuclei have been converted from a difunctional radical to a trifunctional radical, or in terms of the resin, the molecule as a whole has a methylyol-forming reactivity greater than 2. Such shift can take place after the resin has beenformed or during resin formation. Briefly, an example is simply where an alkyl radical, such as methyl, ethyl, propyl, butyl, or the like, shifts from an ortho position to a metaposition, or from a para position to a meta position. For instance, in the case of phenol aldehyde varnish resins, one can prepare at least some in whichthe resins, instead of having only two points of reaction can have three, and possibly more points of reaction, with formaldehyde, or any other reactant which tends to form a methylol or substituted methylol group.

The resins herein employed are soluble in non-oxygenated hydrocarbon solvent, such as benzene or Xylene.

The resins herein employed as raw materials must be comparatively low molal products having an average of 3 to 6 nuclei per resin molecule.

The condensation products here obtained, whether in the form of the free base or the salt, do not go over to the insoluble stage on heating. The condensation product obtained according to the present invention is heat-stable and, in 'fact, one of its outstanding qualities is that it can be subjected to oxyalkylation, particularly oxyethylation or oxypropylation, under conventional conditions, i. e., presence of an alkaline catalyst, for example, but in any event at a temperature above C. without becoming an insoluble mass.

'What 'has been said previously in regard to heat stability, particularly when employed as a reactant for preparation of derivatives, is still important from the standpoint of manufacture of the condensation products themselves insofar that in the condensation process employed in preparing the compounds described subsequently in detail, there is no objection to the employing of a temperature above the boiling point of Water. As a matter of fact, all the examples included subsequently employ temperatures going up to to C.

What is said above deserves further amplification at this point for the reason that it may shorten what is said subsequently in regard to the production of the herein described condensation products. Since formaldehyde generally is employed economically in an aqueous phase (30% to 40% solution, for example) it is necessary to have manufacturing procedure which will allow reactions to take place at the interface of the two immiscible liquids, to wit, the formaldehyde solution and the resin solution, on the assumption that generallythe amine will dissolve in one phase or the other. Although reactions of the kind herein described will begin at least at comparatively low temperatures, for instance, 30 C., 40 C., or 50 0., yet the reaction does not go to completion except by the use of the higher temperatures. The use of higher temperatures means, of course, that the condensation product obtained at the end of the reaction must not be heat-reactive. Of course, one can add an oxygenated solvent such as alcohol, dioxane, various ethers of glycols, or the like, and produce a homogeneous phase. If this latter procedure is employed in preparing the herein described condensations it is purely a matter of convenience, but whether it is or not, ultimately the temperature must still pass within the zone indicated elsewhere, i. e., somewhere above the boiling point of water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims to the procedure employed in the process is not intended to limit the method or order in which the reactants are added, commingled or reacted. The procedure has been referred to as a condensation process for obvious reasons. As pointed out elsewhere it is my preference to dissolve the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However, all three reactants can be added in any order. I am inclined to believe that in the presence of a basic catalyst,

such as the amine employed, that the formaldehyde produces methylol groups attached to the phenolic nuclei which, in turn, react with the amine. It would be immaterial of course, if the formaldehyde reacted with the amine so as to introduce a methylol group attached to nitrogen which, in turn, would react with the resin molecule. Also, it would be immaterial if both types of compounds were formed which reacted with each other with the evolution of a mole of formaldehyde available for further reaction. Furthermore, a reaction could take place in which three different molecules are simultaneously involved although, for theoretical reasons, that is less likely. What is said herein in this respect is simply by way of explanation to avoid any limitation in regard to the appended claims.

'PART 2 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula OH I" OH OH H l 1 Ch H R R 71. R

In the above formula 11 represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., it varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl, heXyl, decyl, or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent 'No. 2,499,365, or in U. S. Patent No. 2,499,368 dated March 7, 1950, to De Groote and Keiser.

if one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated secondary amine as specified, following the same idealized over-simplification previously referrred to, the resultant product might be illustrated thus:

The basic polyamine may be designated thus:

subject to what has been said previously 'as to the presence of at least one secondary amine radical in at least one occurrence of R with the proviso, as previously stated, that the amine radical be other than a primary amine radical, a substituted imidazoline radical or a substituted tetra'hydroprimidine radical. However, if one attempts to incorporate into the formula a structure such as a substituted,polyalkylene amine of the following type:

R! N. CnHIm (CnHInN.D) ,N R! RII in which the various characters have the same significance as in initial presentation of this formula, then one becomes involved in added difiiculties in presenting an overall picture. Thus, for sake of simplicity, the polyamine will be depicted as As has been pointed out previously, as tar as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

in which R is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See pre viously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. it is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although I have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as the 200th of a percent and as much as a few lOths of a percent. Sometimes mod erate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically ever case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. (2., one having just -3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trirner and pentamer present. Thus, the molecular weight may be such that is corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found no reason for using other than those which are lowest in price and most readily available commercially. 'For purposes of convenience suitable resins are characterized in the following table:

TABLE I M01. wt. Ex- Position R of resin ample R of R derived a molecule number from- (based on n+2) Phenyl Para Formal- 3. 5 992. 5

Tertiary butyl 3. 5 882. 5 Secondary butyl. 3. 5 882. 5 Cyclohexylu 3. 5 1,025. 5 Tertiary amyl 3. 5 959. 5 Mixed secondary 3. 5 805. 5

andtertlary amyl.

Tertiary amyl 3. 5 1, 022. 5 Nonyl 3. 5 1, 330. 5 Tertiary butyl 3. 5 1, 071. 5

Tertiary amyl 3. 5 1, 148. 5 Nonyl 3. 5 1, 456. 5 Tertiary butyl 3. 5 1, 008.5

Tertiary amyl 3. 5 1, 085. 5 ony 3. 5 1, 393. 5 Tertiary butyl 4. 2 996. 6

Tertiary amyl 4. 2 1, 083. 4 Nonyl 4. 2 1, 430. 6 Tertiary butyL 4. 8 1, 094. 4 Tertiary amyL. 4. 8 1, 189. 6 Nonyl 4. 8 1, 570. 4 Tertiary amyL... 1. 5 604. 0

all)

TABLE I-Oontinued M01. wt. of resin molecule (based on n+2) R! I I derived n from- Position of R Hexyl do do 1.

.do do Acetalde- 1 Para.-.

men

692. [l 748. O 740. O

m s w '30:! 0CD @0101 Hex Oyolo-hexyl PART 3 As has been pointed out, the amine herein employed as a reactant is a basic secondary polyamine and preferably a strongly basic secondary polyamine free from hydroxyl groups, free from primary amino groups, free from substituted imiclazoline groups, and free from substituted tetrahydropyrimidine groups, in which. the hydrocarbon radicals present, whether monovalent or divalent are alkyl, alicyclic, arylalkyl, or heterocyclic in character. Reference is made to applications Serial Nos. 288,744 and 296,085 for a discussion of the basic secondary polyamines which may be used in producing the compounds used in accordance with the present invention.

By way of example the following formulas are included. It will be noted they include some polyamines which, instead of being obtained from ethylene dichloride, propylene dichloride, or the like, are obtained from dichloroethyl ethers in which the divalent radical has a carbon atom chain interrupted by an oxygen atom:

Another procedure for producing suitable polyamines is a reaction involving first an alkylene iinine, such as ethylene imine or propylene imine, followed by an alkylating agent of the kind described, for example, dimethylsulfate; or else a reaction which involves an alkylene oxide, such as ethylene oxide or propylene oxide, followed by the use of an alkylating agent or the comparable procedure in which a halide is used.

What has been said previously may be illustrated by reactions involving a secondary alkyl amine, or a secondary aralkyl amine, or a secondary alicyclic amine, such as dibutylamine, dibenzylamine, dicyclohexylamine, or mixed amines with an imine so as to introduce a primary amino group which can be reacted with an alkylating agent, such as dimethyl sulfate. ln a somewhat similar procedure the secondary amine of the kind just specified can be reacted with an alkylene oxide such as ethylene oxide, propylene oxide, or the like, and then reacted with an imine followed by the final step noted above in order to convert the primary amino group into a secondary amino group.

Reactions involving the same two classes of reactants previously described, i. e., a secondary amine plus an imine plus an alkylating agent, or a secondary amine plus an alkylene oxide plus an imine plus an alkylating agent, can be applied to another class of primary amines which are particularly desirable for the reason that they introduce a definite hydrophile effect by virtue of an ether linkage, or repetitious ether linkage, are certain basic polyether amines of the formula:

in which x is a small whole number having a value of l or more, and may be as much as 10 or 12; n is an integer having a value of 2 to 4, inclusive; m represents the numeral 1 to 2; and m represents a number to 1, with the proviso that the sum of m plus m equals 2; and R has its prior significance, particularly as a hydrocarbon radical.

The preparation of such amines has been described in the literature and particularly in two United States patents, to Wit, U. S. Nos. 2,325,514 dated July 27, 1943, to Hester, and 2,355,337 dated August 8, 1944, to Spence.

The latter patent describes typical haloalkyl others such CHaO CzHaCl UH -CH2 CH: OH-CH2O CzHlO CQNlBI' Such haloalkyl others can react with ammonia, orwith a primary amine such as methylamine, ethylamine, cyclohexylamine, etc., to produce a secondary amine of the kind above described, in which one of the groups attached to nitrogen is typified by R. Such haloalkyl others also can be reacted with ammonia to give secondary amines as described in the first of the two patents mentioned immediately preceding. Monoamines so obtained and suitable for conversion into appropriate polyamines are exemplified by Other somewhat similar secondary monoamines equally suitable for such conversion reactions in order to yield appropriate secondary amines, are those of the composition as described in U. S. Patent No. 2,375,659 dated May be methyl, ethyl, propyl, amyl, octyl, etc.

Other suitable secondary amines which can be converted into appropriate polyamines can be obtained from products which are sold in the open market, such as may 'be obtained by alkylation of cyclohexylmethylamine or the alkylation of .similar primary amines, or for that matter, amines of the kind described in U. S. Patent No. 2,482,546 dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta-phenoxyethylamine, gamma-phenoxypropylamine, beta-phenoxy-alpha-methylethylamine, and beta-phenoxypropylamine.

Other secondary monoamines suitable for conversion into polyamines are the kind described in British Patent No. 456,517 and may be illustrated by Over and above the specific examples which have appeared previously, attention is directed to the fact that added suitable polyamines are shown in subsequent Table II.

- PART 4 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is diflicult to actually depict the final product of the cogeneric mixture except in terms of the process itself. The condensation of the resin, the amine and formaldehyde is described in detail in applications Serial Nos. 288,744 and 296,085, and reference is made to those applications for a discussion of the factors involved.

Little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration:

Example 1b sponded to an average of about 3 /2 phenolic nuclei, as

the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2-external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a preceding were powdered and mixed with a somewhat lesser weight of xylene, i. e., 600 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 30 to 35 C. and 176 grams of symmetrical dimethylethylene diamine added. The mixture was stirred vigorously and formaldehyde added slowly. in this particular instance the formaldehyde used was a 30% solution and 200 grams were employed which were added in a little short of 3 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 46 C. for about 19 hours. At the end of this time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of unreacted formaldehyde was noted. Any unreacted formaldehyde seemed to dis-,

appear within approximately two to three hours after set so as to eliminate all the Water-of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached approximately 152 C. or slightly higher. The mass was kept at this higher temperature for three to four hours and reaction stopped. During this time, any additional water which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall time for reaction was somewhat less than 30 hours. In other examples, it varied from a little over 20 hours up to 36 hours. The time can be reduced by cutting the low temperature period to approximately 3 to 6 hours.

Note that in Table 11 following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 to 150 C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the Water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table II.

PART

In preparing o-xyalkylated derivatives of products of the kind which appear as examples in Part 3, I have found it particularly advantageous to use laboratory equipment which permits continuous oxypropylation and 3:3 oxyethylation. More specific reference will be made to 8-0 refers to oxyethylation and it is understood that oxypropylation can be handled conveniently in exactly the same manner. The oxyalkylation of the amine resin TABLE II Strength of p Reaction Max.

Ex. No. Resin Amt, Amine used and formaldehyde Solvent used and Reaction time, distill.

used grs. amount solrr. and amt. amt. temp, O. hrs. tegnp 882 Amine A, 176 g 30%, 200 g Xylene, 660 g -23 26 152 480 Amine A, 88 g Xylene, 450 g 20-21 24 150 633 do Xylene, 550 g 20-22 28 151 441 Amine B, 116 g Xylene, 400 g 20-28 30 144 480 do Xylene, 450 g 22-30 156 633 do Xylene, 600 g 21-28 32 150 882 Amine C, 204 g. Aldo 21-23 145 480 Amine O, 102 g. I, 20-25 148 d d Xylene, 500 g 20-27 35 143 37%, 81 g Xylene, 425 g 20-22 31 145 d Xylene, 500 g 21-26 2/1 146 Xylene, 550 g. 22-25 36 151 Xylene, 400 g. 25-38 32 150 do a- 21-24 30 152 21-26 27 145 20-23 25 141 22-27 29 143 23-25 36 149 do 21-26 32 148 do 21-23 30 148 do 20-26 36 152 do 21-24 32 150 Amine H, s1 21-22; 25 150 391 Amine H, 141 g 30%, r; 21-22 as 151 As to the formulas of the above amines referred to as Amine A through Amine H, inclusive, see immediately below:

condensates is carried out by procedures which are commonly used for the oxyalkylation of oxyalkylation susceptible materials. The factors to be considered are discussed in some detail in applications Serial Nos. 301,805 and 310,553 and reference is made to those applications for a description of suitable equipment, precautions to be taken and a general discussion of operating technique.

The following examples are given by way of illustration.

Example 1c The oxyalkylation susceptible compound employed is the one previously described and designated as Example lb. Condensate lb was in turn obtained from symmetrical dimethyl-ethylene diamine and the resin previously identified as Example 211. Reference to Table I shows that this particular resin is obtained from Paratertiarybutylphenol and formaldehyde. 10.82 pounds of this resin condensate were dissolved in 6 pounds of solvent (xylene) along with one pound of finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave 'to operate at a temperature of approximately 125 C. to 120 C., and at a pressure of about 15 to 20 or 25 pounds, 25 pounds at the most. In some subsequent examples pressures up to 35 pounds were employed.

The time regulator was set so as to inject the ethylene oxide in approximately three-quarters of an hour and then continue stirring for 15 minutes or longer, a total time of one hour. The reaction went readily and, as a matter of fact, the oxide was taken up almost immediately. Indeed the reaction was complete in less than an hour. The speed of reaction, particularly at the low pressure, undoubtedly due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit. 10.82 pounds. This represented a molal ratio of 24.6 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was 2164. A comparatively small sample,

less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned and also for the purpose of making some tests on various oil field emulsions. The amount Withdrawn was so small that no cognizance of this fact is included in the data, or subsequent data, or in the data presented in tubular form in subsequent Tables III and IV.

The size of the autoclave employed was 25 gallons. In innumerable comparable oxyalkylations I have withdrawn a substantial portion at the end of each step and continued oxyallrylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a difierent oxide.

Example 2c This example simply illustrates the further oxyalkylation of Example 10, preceding. As previously stated, the oxyalkylation-susceptible compound, to wit, Example lb, present at the beginning of the stage was obviously the same as at the end of the prior stage (Example to wit, 10.82 pounds. The amount of oxide present in the initial step was 10.82 pounds, the amount of catalyst remained the same, to wit, one pound, and the amount of solvent remained the same. The amount of oxide added was another 10.82 pounds, all addition of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 21.64 pounds and the molal ratio of ethylene oxide to resin condensate was 49.2 to l. The theoretical molecular weight was 3246.

The maximum temperature during the operation was 125 C. to 130 C. The maximum pressure was in the range of to 25 pounds. The time period was one and three-quarter hours.

Example 30 The oxyalkylation proceeded in the same manner de scribed in Examples 1c and 2c. There was no added solvent and no added catalyst. The oxide added was 10.82 pounds and the total oxide at the end of the oxyethylation step was 32.46 pounds. The molal ratio of oxide to condensate was 73.8 to 1. Conditions as far as temperature and pressure and time were concerned were all the same as in Examples 10 and 2c. The time period was somewhat longer than in previous examples, to wit, 2 hours.

Example 40 The oxyethylation was continued and the amount of oxide added again was 10.82 pounds. There was no I 14 added catalyst and no added solvent. The theoretical molecular weight at the end of the reaction period was 54.10. The molal ratio of oxide to condensate was 98.4 to 1. Conditions as far as temperature and pressure were concerned were the same as in previous examples. The time period was slightly longer, to wit, 2 /2 hours. The reaction unquestionably began to slow up somewhat.

Example 50 i The oxyethylation continued with the introduction of another 10.82 pounds of ethylene oxide. No more solvent was introduced but .3 pound caustic soda was added. The theoretical molecular weight at the end of the agitation period was 64.92, and the molal ratio of oxide to resin condensate was 123 to 1. The time period, however, dropped to 2 hours. Operating temperature and pressure remained the same as in the previous example.

Example 60 The same procedure was followed as in the previous examples. The amount of oxide added was another 10.82 pounds, bringing the total oxide introduced to 64.92 pounds. The temperature and pressure during this period were the same as before. There was no added solvent. The time period was 3 hours.

Example 7c The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 75.74 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 8656. The time required for the oxyethylation was a bit longer than in the previous step, to wit, 4 hours.

Example So This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 86.56 pounds. The theoretical molecular weight was 9738. The molal ratio of oxide to resin condensate was 196.8 to one. Conditions as far as temperature and pressure were concerned were the same as in. the previous examples and the time required for oxyethylation was 5 hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables III and IV, V and VI.

In substantially every case a 25-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a 15-gallon autoclave and then transferred to a ZS-gallon autoclave. This is immaterial but happened to he a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables III and IV, it will be noted that compounds 10 through 40:: were obtained by the use of ethylene oxide, whereas 410 through cwere obtained by the use of propylene oxide alone.

Thus, in reference to Table III it is to be noted as follows:

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to wit, the resin condensate, is indicated in the second column.

The amount of condensate is shown in Assuming that ethylene .oxide alone is employed, as.

happensto be the case in Examples 1c through 40c, the

amount of oxide present in the oxyalkylation derivative is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

The 8th column can be ignored where a single oxide was employed.

The 9th column shows the theoretical molecular Weight at the end of the oxyalkylation period.

The 10th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 10 coincides with the figure in column 3.

Column 11 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period.

Column 12 can be ignored insofar that no propylene oxide was employed.

Column 13 shows the catalyst at the end of the reaction period.

Column 14 shows the amount of solvent at the end of the reaction period.

Column 15 shows the molal ratio of ethylene oxide to condensate.

Column 16 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table IV. It is to be noted that the first column refers to Examples 1c, 2c, 30, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with several volumes of water, xylene and kerosene. It sometimes happens that although xylene in comparatively small amounts will dissolve in the concentrated material when the concentrated material in turn is diluted with xylene separation takes place.

Referring to Table IV, Examples 410 through 800 are the counterparts of Examples 10 through 400, except that the oxide employed is propylene oxide instead of ethylene oxide. Therefore, as explained previously, four columns are blank to wit, columns 4, 8, 11 and 15.

Reference is now madeto Table V. It is to be noted these compounds are designated by d numbers, 1d, 2d, 3d, etc., through-and including 32d. They are derived, in turn, from compounds in the c series, for example, 360, c, 54c and 70c. These compounds involve the use of both ethylene oxide and propylene oxide. Since compounds 10 through 400 were obtained by the use of ethylene oxide, it is obvious that those obtained from 36c and 400, involve the use of ethylene oxide first, and propylene oxide afterward. Inversely, those compounds obtained from 54c and 700 obviously come from a prior series in which propylene oxide was used first.

In the preparation of this series indicated by the small letter d, as 1d, 2d, 3d, etc., the initial c series such as 36c, 40c, 54c, and 70c, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may have been the case in the original oxyalkylation step. Then oxyalkylation proceeded by using the second oxide as indicated by the previous explanation, to wit, propylene oxide in 1d through 16d, and ethylene oxide in 17a through 32d, inclusive.

In examining the table beginning with 1d, it will be noted that the initial product, i. e., 36c, consisted of the reaction product involving 10.82 pounds of the resin condensate, 16.23 pounds of ethylene oxide, 1.0 pounds of caustic soda, and 6.0 pounds of the solvent.

It is to be noted that reference to the catalyst in Table V refers to the total amount of catalyst, i. e., the catalyst present from the first oxyalkylation step plus added catalyst, if any. The same is true in regard to the solvent. Reference to the solvent refers to the total solvent present, i. e., that from the first oxyalkylation step plus added solvent, if any.

In this series, it will be noted that the theoretical molecular weights are given prior to the oxyalkylation step, although the value at the end of one step is the value at the beginning of the next step, except obviously at the very start the value depends on the theoretical malecular weight at the end of the initial oxyalkylation step; i. e., oxyethylation for 1:! through 16d, and oxypropylation for 17d through 32d.

It will be noted also that under the molal ratio the values of both oxides to the resin condensate are included.

The data given in regard to the operating conditions is substantially the same as before and appears in Table VI.

The products resulting from these procedures may contain modest amounts, or have small amounts, of the solvents as indicated by the figures in the tables. If desired the solvent may be removed by distillation, and particularly vacuum distillation. Such distillation also may remove traces or small amounts of uncombined oxide, if present and volatile under the conditions employed.

Obviously, in the use of ethylene oxide and pyropylene oxide in combination one need not first use one oxide and then the other, but one can mix the two oxides and thus obtain what may be termed an indifferent oxyalkylation, i. e., no attempt to selectively add one and then the other, or any other variant.

Needless to say, one could start with ethylene oxide and then use propylene oxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, and then go back to propylene oxide; or, one could use a combination in which butylene oxide is used along with either one of the two oxides just mentioned, or a combination of both of them.

The colors of the products usually vary from a reddish amber tint to a definitely red, and amber. The reason is primarily that no efifort is made to obtain colorless resins initially and the resins themselves may be yellow, amber, or even dark amber. Condensation of a nitrogenous product invariably yields a darker product than the original resin and usually has a reddish color. The solvent employed, if xylene, adds nothing to the color, but one may use a darker colored aromatic petroleum solvent. Oxylkylation generally tends to yield lighter colored products and the more oxide employed the lighter the color of the product. Products can be prepared in which the final color is a lighter amber with a reddish tint. Such products can. be decolorized by the use of clays, bleaching chars, etc. As far as use in demulsification is concerned, or some other industrial uses, there is no justification for the cost of bleaching the product.

Generally speaking, the amount of alkaline catalyst present is comparatively small and it need not be removed. Since the products per so are alkaline due to the presence of a basic nitrogen, the removal of the alkaline catalyst is somewhat more difficult than ordinarily is the case for the reason that if one adds hydrochloric acid, for example, to neutralize the alkalinity one may partially neutralize the basic nitrogen radical also. The preferred procedure is to ignore the presence of the alkali unless it is objectionable or else add a stoichiometric amount of concentrated hydrochloric acid equal to the caustic soda present.

The conversion of the oxyalkylated basic condensates of the kind previously described into the corresponding salt of gluconic acid is a simple operation since it is nothing more nor less than neutralization. The condensate invariably contains two basic nitrogen atoms. One can neutralize either one or both nitrogen atoms.

Another factor which requires some consideration would be the presence of basic catalysts which were used during the oxyalkylation process. Actual tests indicate that the basicity appears to be somewhat less than would be expected, particularly in examples in which oxyalkylation is comparatively high. The usual procedure has been to add enough gluconic acid to convert the product into the salt as predetermined and then note whether or not the product showed any marked alkalinity. If so,

slightly more gluconic acid was added until the product was either just barely acid or just very moderately alkaline. For sake of clarity this added amount of gluconic acid, if required, is ignored in subsequent Table VIII.

Gluconic acid is available as a 50% solution. Dehydration causes decomposition. This is not true of the salts, or at least, the salts of the herein described oxyalkylated condensates. Such salts appear to be stable, or stable for all practical purposes, at least at a temperature slightly above the boiling point of water and perhaps at a temperature as high as 150 C. or thereabouts.

Max. Max. Solubility Ex. tern pres., Time, No. p. 8.1. hrs.

Kerosene 30-35 Soluble. 30-35 Do. 30-35 Do. 30-35 D0. 15-20 Insoluble 15-20 D0. 15-20 Do. 15-20 Do. 15-20 D0. 15-20 Soluble. 15-20 Do. 15-20 Do.

-10 Insoluble 5-10 Do. 5-10 Do. 5-10 Soluble. 5-10 D0. 5-10 Do. 5-10 Do. 5-10 Do. -20 Insoluble 15-20 D0. 15-20 D0. 15-20 D0. 15-20 D0. 15-20 Soluble. 15-20 D0. 15-20 D0. -30 Insoluble 20-30 Do. 20-30 D0. 20-30 Do. 20-30 Do. 20-30 D0. 20-30 Do. 20-30 Soluble 20-30 Insoluble 20-30 D0. 20-30 Do. 20-30 Do. 20-30 Do. 20-30 D0. 20-30 Do. 20-30 Do. -35 Soluble. 30-35 Do. 30-35 Do. 30-35 D0. 30-35 Dlsperslble. 30-35 oluble. 30-35 Do. 30-35 Do. 5-10 Soluble. 5-10 Do. 5-10 Do. 5-10 Do. 5-10 Do. 5-10 Dlsperslble. 5-10 Insoluble. 5-10 Do.

PART 6 As has been pointed out previously the present apphcation is a continuation-in-part of certain co-pending applications and reference is made to aforementioned copending application, Serial No. 329,484, filed January 2, 1953. The co-pending application, Serial No. 329,484, filed January 2, 1953, describes the neutralization of the nonoxyalkylated condensate.

Reference now is made to Table VII which, in essence, is substantially the same as much of the data in Table II but includes additional calculations showing the amount of gluconic acid required to neutralize a certain amount of condensate; for instance, compare Example 1e in Table VII, with Example 1b in Table II. In any event, since there were available various oxyalkylated derivatives of condensates 1b and 10b these particular oxyalkylated derivatives were used for the purpose of illustrating a salt formation, all of which is illustrated in Table VIII.

Briefly stated, referring to Example la in Table VII it is to be noted that 1082 grams of the nonoxyalkylated condensate required 1572 grams of 50% gluconic acid for neutralization. Reference to Table VIII shows that 1082 grams of the condensate Example 1b, when converted into the oxyalkylated derivative as obtained from 20, were equivalent to 3875 grams. Therefore, 3875 grams were selected as the appropriate amount of oxyalkylated material for neutralization simply for the reason that calculation was eliminated.

tion invariably is lighter than the initial material for the reason that the condensate is dark colored and oxyalkylation simply dilutes the color. In other words, the product may be almost white, pale straw color, or an amber shade with a reddish tint.

The product either before or after neutralization can be bleached with filtering clays, charcoals, etc. The procedure generally is, as a matter of convenience, to form the salt and then dilute with a solvent if desired, using such solvent as xylene or a mixture of two-thirds xylene and one-third ethyl alcohol or isopropyl alcohol, to give approximately a 50% solution. If there happened to be any precipitate the solution is filtered. If desired, the product prior to dilution could be rendered anhydrous simply by adding benzene and subjecting the mixture to reflux action under a condensate or a phase-separating trap. If there happened to be any tendency for the prodnet to separate then the solvents having hydrotropic properties, such as the diethylether of ethyleneglycol, or the like are used.

The salt formation is merely a matter of agitation at room temperature, or at a somewhat higher temperature if desired, particularly in a reflux condenser. Usually agitation is continued for an hour but actually neutralization may be a matter of minutes. In some instances after salt formation is complete and the product is diluted to approximately 50%, I have permitted the solution to stand for about 6 to 72 hours. Sometimes, de pending on composition, there is a separation of an aqueous phase or a small amount of salt-like material. On a laboratory scale the procedure is conducted in a separatory funnel. If there is separation of an aqueous phase, or any other undesirable material, at the bottom of the separatory funnel it is merely discarded. The salt form, of course, can be bleached in the same manner as previously described for the oxyalkylated derivative. Usually the color of the salt is practically the same as the oxylaiaylated derivative. For various commercial purposes in which the product is used there is no justi fication for the added cost of decolorization. The salt form can be dehydrated or rendered solvent-free by the usual procedure, i. e., vacuum distillation, after the use of a phase-separating trap.

The product as prepared, without attempting to decolorize, eliminate any residual catalyst in the form of a salt, and without any particular effort to obtain absolute neutrality or the equivalent, is more satisfactory for a number of purposes where the material is useful, such as a demulsifier for petroleum emulsions of the water-inoil type, or oil-in-water type; or in the prevention of corrosion of metallic surfaces, especially ferrous surfaces; or as an asphalt additive for anti-stripping purposes.

The condensates prior to oxyalklyation may be solids but are generally viscous liquids or liquids which are almost solid or tacky. Oxyalkylation reduces such materials to viscous liquids or thin liquids comparable to polyglycols, of course depending primarily on the amount of alklene oxide added. After neutralization the physical characteristics of the products are about the same and in the majority of cases are liquids. if a solvent were added, even if the material were solid initially, it would be converted into a liquid form.

In light of what has been said and they simplicity of salt formation it does not appear that any illustration required. However, previous reference has been made to Table Vlll. The first example in Table VIII is Example 1 The following is more specific data in regard to Example If; Example If The salt was made from oxyalkylated derivative Example 2c. Oxyalkylated derivative 20, in turn, was made from condensate 1b; condensate 1b, in turn, was made from resin Example 241 and symmetrical dimethylated ethylene diamine. 882 grams of the resin were dissolved in approximately an equal weight of Xylene and reacted with 176 grams of the amine and 200 grams of 30% formaldehyde. All this has been described previously. The weight of the condensate on a solvent-free basis was 1082 grams. This represented approximately 56 grams of basic nitrogen. Referring to Table VIII it wiil be noted that 10.32 pounds of condensate were combined in 21.6 pounds of ethylene oxide, in combination with 6 pounds of solvent. In any event 3875 grams of the oxyalkylated derivative 2c were placed in a laboratory device which, although made of metal, was the equivalent of a separatory funnel. To this there were added 1572 grams of gluconic acid and the mixture stirred vigorously for an hour and allowed to stand at room temperature, or thereabouts for approximately 2 /2 days. The slight amount of dregs at the bottom was withdrawn and the material storcd as such, although it was diluted to approximately 50% with xylene and employed in the form of a 50% solution. A number of other examples are included in Table VIII.

For convenience, Table VII is included at this point just preceding Table VIII.

TABLE VII Salt formation calculated on Condensate in turn derived trombasis of non-oxyalkyla'ted 11; condensate from Salt cond 37% Wt. of N0. sate Amt. Amt. Amine formconden- Theo. 50% glu- No. Resin resin, Solvent sol- Amine used 1 used, aldesate on basic conic No. grns. vent, gms. hyde, solventnitrogen, acid, gms. gms. free basis, gms. gins.

gms.

176 I 200 1, 082 56.0 1, 572 88 Z 580 28. 0 786 88 9 100 733 28.0 786 116 81 569 28. 0 786 116 81 608 28. 0 786 116 81 j 761 28. 0 786 204 1 200 1, 56. 0 1,572 102 2 100 594 28. 0 736 102 2 100 747 28.0 786 117 81 602 37. 5 l, 050 117 81 6 10 37. 5 7, 050 117 81 794 37. 5 1,050 176 2 200 1,082 56.0 1, 572 116 81 569 28.0 393 204 2 200 l, 110 56.0 786 1 For identification of amines see notes immediately following Table II.

9 30% Formaldehyde.

Needless to say,

TABLE VIII Grams ofoxyalkylated compound Percent which is equiv. 50 percent Oxyalkylcondento grams of congluconic N Bled sate in densate acid to rlvative, oxyalkylneutralex. N 0. ated tieice, grams Oonden- Amt. con- EtO PrO Solvent rlvative Oxyalkyl- Condensate, clensate, amt., amt, amt ated comsate ex. N 0. lbs. lbs. lbs. lbs. pound PART 7 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon .tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of my process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even to to 40,000 or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within suchconcentrations. This same fact is true in regard to the material or materials of my invention when employed as demulsify-' ing agents.

The materials of my invention, when employed as treating or demulsifying agents, are used in the conventional way, well known to the art, described, for example, in Patent 2,226,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous, and down-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mixture to stratify.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

Gluconic acid salt, for example, the product of Example 1f, 20%;

A cyclohexylamine salt of a polypropylated napthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated napthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sultonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol, 5%.

The above proportions are all weight percents.

PART 8 The gluconic acid salts herein described can be used as emulsifying agents for oils, fats and waxes; as ingredicuts in insecticide compositions; or as detergents and wetting agents in the laundering, scouring, dyeing, tanning and mord-anting industries. They also can be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes. Also, the gluconic acid salts are useful in dry cleaners soaps.

Also, they may be used as additives in connection with other emulsifying agents; they may be used to contribute hydrotropic effects; they may be used as anti-strippers in connection with asphalts; they may be used to prevent corrosion particularly the corrosion of ferrous metals for various purposes and particularly in connection with the production of oil and gas, and also in refineries where crude oil is'converted into various commercial products. The products may be used industrially to inhibit or stop microorganic growth or other objectionable lower forms of life, such as the growth of bacteria, molds, etc; they are valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils, and also to hydraulic brake fluids of the aqueous or nonaqueous type; some have definite anti-corrosive action. They may be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters.

After oxyalkylation a condensate of the kind previously described becomes a derivative which retains basic nitrogen radicals and also includes alkanol radicals, such as the hydroxyethyl or hydroxypropyl radical. Thus, in attempting to dehydrate the oxyalkylated salt derivative from gluconic acid or merely by heating there may be a rearrangement wherein one forms the ester in the same manner that triethanolarnine oleate can be converted into oleyl triethanolamine. Thus the compounds described may serve as precursors for other derivatives obtained by an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forrning reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the'amino nitrogen atom with a resin molecule; and with the further proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

2, A three-step manufacturing process including the method of first condensing (a) an oxyalkylation-suscepti ble, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which -R is an aliphatic hydrocarbon radical having at least-4 and not more than 24 carbon atoms and'substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached 'toany amino nitrogen atom, and with the further proviso that the polyarnine be free from any primary amino radical, any substituted irnidazoline radical and any substituted tetrahydropyrimidine radical, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the further proviso that the molar ratio of reactants be approximately 1, 2 and 2 respectively; and with the final proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

3. A three-step manufacturing process including the method of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the .ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbonatoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

4. A three-step manufacturing process including the method of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin 29 having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and formaldehyde; said condensation reaction being con ducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that themolar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

5. A three-step manufacturing process including the method of first condensing(a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per. resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and sub- 30 tion reaction be conducted so as to produce a significan portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehydederived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methyl-glycide; and followed by the third step of neutralizing with gluconic acid.

-6. A three-step manufacturing process including the method of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difun-ctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohyd'ric phenol and formaldehyde; said resin being formed in the substantial absence of trifun-ctional phenols; said phenol being of the formula.

in which R is a para-substituted aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms; ([2) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and (c) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below '150" C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a form-aldehydederived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and 'methylglycide; and followed by the third step of neutralizing with glucon'ic acid.

7. The manufacturing procedure of claim 1 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

8. The manufacturing procedure of claim 2 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

9. The manufacturing procedure of claim 3 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination. r

10. The manufacturing procedure of claim 4 wherein r I51 32. the oxyalkylation step is limitedto the use of both ethyl- 13. The product resulting from the three+step manuene oxide and propylene oxide in combination. facturing procedure defined in claim-1. 11. The manufacturing procedure of claim 5 wherein the oxyalkylatien step is limited to the use of both ethyl- References Cited in the file of this patent ene oxide and propylene oxide in combination.

12. The manufacturing procedure of claim 6 wherein UNITED STATES PATENTS the oxyalkyla'tion step is limited to the use of both ethyl- 2,031,557 Bruson Feb. 18; 1936 ene oxide and propylene oxide in combination. 2,743,253 De Groote Apr. 24, 1956 

1. A THREE-STEP MANUFACTURING PROCESS INCLUDING THE METHOD OF FIRST CONDENSING (A) AN AOXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENERATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DICUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 